Polymerizable and polymerized compositions comprising an allylmelamine or allylisomelamine



United States Patent POLYMERIZABLE AND POLYMERIZED COMPO- SITIONSCOMPRISING AN ALLYLMELAMINE OR ALLYLISOMELAMINE v Walter M. Thomas,Springdale, Conm, assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Application October 28, 1952,

. Serial No. 317,370

21 Claims. (Cl; 260-855) This application is a continuation-in-part ofmy copending application-Serial No. 234,468, filed June 29, 1951, andnow abandoned.

This invention relates to the production of new synthetic materialshaving'valuable' and characteristic properwhere at least one and notmore than three of the Rs represent the radical CH2-CH=CHz and theremainingRs are a member of the class' consisting of hydrogen andalkyl,cycloalkyl, aryl (including alkaryl) and aralkyl radicals, and (b)isomelamines corresponding to the melamines of (a), and (2) a'substancewhich is different from the compound of (l), which copolymeriz'abletherewith, and which is selected from the class of unsaturatedsubstances consisting of (A) compounds containing a CHz=C grouping, (B)unsaturated alkyd resins produced by reaction of ingredients comprisinga polyhydric alcohol and an ethylenically unsaturated polycarboxyliccompound, and (C) mixtures of (A) and (B), the compound of (1)constituting from about 1% to about 75% by weight of the total amount of(1) and (2 Examples of suchpolymerizable compositions are those whereinthe substance of (2) is a vinyl compound, more particularly a vinylaliphaticcompound (e. g., acrylonitrile, acrylic esters, acrylamide,etc.), or a vinyl aromatic compound, e. g., styrene, etc., within theaforementioned proportions by weight, for instance in proportions suchthat the compound of (1) constitutes from about 1% .to

about by weight of the total amount of (1) and (2 J.

The scope of the invention also includes products comprising thepolymerized compositions obtained by polymerization of theaforementioned polymerizable compositions, e. g'., a copolymer ofa'mixture of copolymerizable ingredients including acrylonitrile [orother unsaturated substance of the kind broadly described under (2),supra] and a compound (or a plurality of compounds) of the kind embracedby Formula I, in'the aforementioned proportions'by weight,-e. g., in aweight ratio of from about 1% to about 20% (more particularly from about1 or 2% 2,712,004 Patented June 28, 1955 ice formula represents are:alkyl (e. g., methyl, ethyl, propyl,

isopropyl, butyl, secondary-butyl, pentyl, hexyl to dodecyl, etc.);cycloalkyl (e. g., cyclopentyl, cyclohexyl, cycloheptyl, etc.); aryl (e.g., phenyl, diphenyl or xenyl, naphthyl, etc.), including alkaryl (e.g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl,tert.-butylphenyl, etc.); and aralkyl (e. g., benzyl, phenylethyl,phenylisopropyl, etc.)

Melamines of the kind embraced by Formula I and the correspondingisomelamines, which compounds are used in producing the new copolymersof the present invention, can be-made by various known methods. Thus,the melamines can be prepared by methods such as are generally describedin Patent No; 2,361,823. Allylisomelamines used in practicing thepresent invention, more particularly substituted isomelamines containingat least one and not more than three allyl radicals, likewise can beprepared inany suitable manner. For instance the monoallyl derivativescan be produced by methods such as are described in Patent No.2,481,758; and the polyallyl derivatives,

specifically the triallyl derivatives, can be produced as; described in,for example, Beilstein 26, 251.

There is considerable uncertainty as to the exact structural formula ofthe isomelamines, Taking monoallylisomelamine as illustrative of themono-substituted isomelamines used in practicing the present invention,the formula for this compound may be written either as II H It will beunderstood, of course, that in these formulas for the monoallylderivatives used in carrying my invention into efiect, the'hydrogen atomattached to the imino nitrogen atom, aswell as either or both of thehydrogen atoms attached to the amino nitrogen atoms, can be replaced bya radical corresponding to the radical represented by R in Formula I.The formula for triallylisomelamine, which also can be used inpracticing my invention, is believed to be as follows:

' In the imino (='NH) groupings in Formula IV the hydro to about 10 or15%) of the allylmelamine or allylisomelamine (or mixtures thereof) tofrom about 99% to about (more particularly from about 98 or 99% to aboutor of the unsaturated substance of (2),-supra; The scope of theinvention further includes methods of preparing such products.

gen atom of 'any or all'of these groupings can be replacedby a radicalcorresponding to R in Formula I to yield substitutedtriallylisomelamines that also can be used as comonomers in producingthe new copolymers of my invention.

It is one of the primary objects of the present invention to prepare anew class of copolymers for use in industry.

Another object of'the invention is to provide polymerizable orpotentially polymerizable molding and other compositions which have goodstorage stability and which can be handled without difficulty prior toand during fabrication.

-Still another object ,of theinventioniis to prepare .syn theticmaterials which are particularly useful as coating, impregnating,adhesive, laminating andsimilar compositions, and as components .of'such compositions.

Another object of the invention is to :prepare molding compositions fromwhich can be produced clear, molded or :translucent molded articleshaving a wide variety'ot' domestic and industrial applications.

Another object of the invention is-to prepare clear and colorless castarticles, as .wellas laminatedmoldings having high strengthcharacteristics combined with 1 other I .desirable-lproperties.

Another object of the ,inventionis to improve the use fulness -.0fallylniclarnines andallylisomel-amines of the kind-embraced *byformulaflWhCIEbYTthfiif'fifild of utility is enhanced.

.Still another, and one of the most important objects oftheipresentinvention, .is .theproductioniofnew acrylonltrile .copolymercompositions which are -more readily dyed esprecially with acid dyes,than homopolymeric acrylonitrile or many ofzthccopolymersof,acrylonitrilc and another monomer ,or monomers that were{known 1or;suggested prior tomy hivention.

Another :object of the invention .is :to :prepare such copolymers whichcan bespun or otherwise shaped to form filaments, tapes, ribbons,tubesyrodsnsheets, etc., and the shaped articles :then .dyed eitherbefore or after having been oriented or treated to improve their .useful,properties.

Other objects of the invention will be apparent to those skilled in theart from the description and examples which follow.

These objects are accomplished, in general, by preparing a copolymer ofthe aforementioned ingredients, in the weight proportions hereinbeforestated, by any suitable means. The copolymer advantageously is produced,for instance, by polymerizing the mixture of unsaturatedrnaterials withthe aid of a polymerization catalyst or catalysts. In certain cases. forexample, when acrylonitrile is the unsaturated material thatis=copolymerized with the allylmelamine.or'allylisomelamine. thepolymerization can advantageously be effected in an aqueous medium, withthe aid of a polymerization catalyst or catalysts; and, at the end ofthe polymerization period, isolating the resultinglcopolymer.

Examples .of monomers containing a .CH2=C :group ing-that can becopolymerized 'w'itha compound .of the i kind-embraced by Formula I,which are different therefrom, and which can he polymerized eithersinglycra plurality (two, three, four or.anydesirednumber) thereof, thelatterioften being desirablein order ,to improve the patibility andcopolymerization characteristicsof-the I??? mixture of monomers and toobtain new and :valuable copolymers having the particular propertiesdesired for a particular service application, are such monomers as theunsaturated alcohol esters, more particularly the allyl, methallyl,.erotyl, 'l-chloroallyl, 2 'chloroallyl, cinnamyl, vinyl, methvinyl,l-phenylallyl, butenyl, etc., esters of saturated and unsaturated,aliphatic and aromat c, monobasic and polybasic acids such, forinstance, as acetic, propionic, butyric, valeric, caproic, acrylic andalpha-substituted acrylic (inclndingalkacrylic, .e. ,g., methacrylic,.ethacrylic, propacrylic, etc, andar-ylaerylic, e. g., phenylaerylic,etc .crotonic, .oxalic, malonic, succinic,

,glutaric, adipic, pimelic, 'suberic, azelaic, .sebacic, maleic,

fumaric, citraconic, :mesaconic, itaconic, acetylene dicarboxylic,aconitic, benzoic, phenylacetic, ;phth alic, terephthalic,benzoylphthalic, etc, acids; the saturated monohydric alcohol esters, e.g., the methyl, ethyl, propyl, isopropyl, butyl, sec.-bntyl, amyl, etc.,esters of unsaturated aliphatic monobasic and polybasic acids,,illustrative examples of which appear above; vinyl cyclic compounds(including monovlnyl aromatic hydrocarbons),

c. g., styrene, 0-, m-, and p-chlorostyrenes, -br0mosty-' renes,-fluorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes, thevarious poly-substituted styrenes such, for example, as the variousili-, :triand tetra-chlorostyrenes, -bromostyrenes, -fluorost-yrenes,.-methylstyrenes, -ethylstyrenes, cyanostyrenes, .etc., vinylnaphthalene, vinylcyclohexane, vinyl furane, :vinyl pyridine,vinyldibenzofuran, divinyl benzene, trivinyl benzene, allyl benzene,diallyl benzene, N-vinyl'carbazole,-the-various allyl cyanostyrenes, the*various alpha-substituted:styrenes and alpha-substitutedring-substituted styrenes, e. g., alphamethyl styrene,alpha-methyleparraemethyl, etc.; unsaturated ethers, e. g., ethyl vinylether, diallyl ether, ethyl methallyl ether, etc.; unsaturated amides,for instance N-allyl caprolactam, acrylamide, and 'N-snbstitutedacrylamides, e..g., N-methylol .acrylamide, N-allyl acr-ylamide,Nanethyl acrylamide, -N-phenyl acrylamide, etc.; unsaturated ketones, e.g., methyl vinyl-ketone, methyl allyl laetone, etc.; methylene .maloniclesters, ,e. ;g. methylene methyl malonate, etc.; ethylene; butadienes,.e. 4;. 1,3- butadiene, 2-chlorobutadiene, etc.; unsaturated polyhydricalcohol .(e.;g., butenedioL-etc.) esters ofsaturated and.unsaturated,aliphatic and aromatic, smonobasic and :polytag-sic acids, illustrativeexamples-of which appear above.

Other examples of monomers that'can be copolymerized with an.allylrnelamineor allyl isomelramine Lof the kind embraced by Formula Iare the vinyl halides, more particularly vinyl fluoride, vinyl chloride,vinyl bromide and vinyl iodide, and the various vinylidene compounds,including the vinylidene halides, e. g., vinylidene chloride, vinylidenebromide, vinylidene fluoride and vinylidene iodide, other ,comonomers.beingadded if needed in order to improve the compatibility andcopolymerization characteristics of the mixed monomers.

Other and more specific examples of monomeric materials which may bemixed orblended with thecompound ofiFormula Land the resultinghomogencous or substantially homogeneous, polymerizible composition thenpolymerized, ashereinaftermorerfullyidescribcdto yield new and valuable.copolymerzcompositions are .therallyl compounds which are differentfrom the allyl compound embraced by Formula I and especiallytthose whichhave a boiling point-.ofat least about 60 C. Of the monoterm alargeclass, all of ewhichare suitable. The reactive .allyl compounds employedare preferably those which have .a high =boiling,point :suchg-forexample. as diallylmaleate, diallyl'fumarate, cliallyl,phthalate diallylsuccinate, =etc. Other 'allyl compounds which are not necessarilyghighboiling also may be iused.

More specific examples of rally] compounds :that can lac copolymerizedwith ithe allyl ,compound of formula I are allylalcohol, methallylalcohol, allyl acetate. allyl methacnylate, ,diallyl carbonate,allyldactate. ,allyl alphahydroxyisobutyrate, :a'llyl trichlorosilane,ally! ,acrylatc, diallyl imalonate, diall-yboxalatc, ,diallylgluconate,diallyl methyjlgluconate, .diallyl gadipate, -.diallyl tazelate, diallylsehacate, diallyl itartronate, diallyl ltartrate, .dia'llyl mesaconate,-.diallyl .citraconate, the=diallyl ester of 'muconic acid, diallyl:itaconate, ,diallyl .ehlorophthalate.-.diallyl .dichlorosilane, .the=diallyl Iester of iendornethylene tetrahydrophthalic zanhydridc,.triallyl -.t;ricarballylate, triailyl aconitate, :triallyl cyanuratc,atriallyl citrate, rtriallyl ;;phos phate, trimethallyl ,phosphate,:tetrallyl siiane, tetrallyl silicate, :hexallyl disiloxanc,etc. Otherexamples'of allyl compounds-,thatmay be.employedareggiven,. foiuexamplc,in Kropa P,-atent 'No. 2;5 lQ,503 issued June 6. 19-50.

Among .thelcomonomers ,which are preferred ,for use in carrying myinvention into-elfect areithe vinyl 2.60111- pounds, including the:vinyl aromatic compounds, more particularly the vinyl .aromatichydrocarbons rte. styrene, ithe variouspdinlkylzstyrenes,ietc andthcNI-[1Y1 aliphatic ecompollnds, -e.;g. ;ac13y lonitrile,.acrylamide, etc,and other compounds containing:a ECH2:,C grouping,

6. g., the various substituted acrylonitriles (e. g., methacrylonitrile,ethacrylonitrile, phenylacrylonitrile, etc.), the various substitutedacrylamides (e. g., methacrylamide, ethacrylamide, the variousN-substituted acrylamides and alkacrylamides, for instance N-methylolacrylamide, N- monoalkyl and -dialkyl acrylamides and methacrylamides,e. g., N-monomethyl, -ethyl, -propyl, -butyl, etc., and N-dimethyl,-ethyl, -propyl, -butyl, etc., acrylamides and methacrylamides,N-monoaryl and -diaryl acrylamides and alkacrylamides, e. g.,N-monophenyl and -diphenyl acrylamides and methacrylamides, etc.), vinylesters, e. g., vinyl acetate, vinyl propionate, vinyl butyrate, vinylisobutyrate, vinyl valerate, vinyl acrylate, vinyl methacrylate, etc.,esters of an acrylic acid (including acrylic acid itself and the variousalpha-substituted acrylic acids, e. g.,

methaorylic acid, ethacrylic acid, phenylacrylic acid,.

etc), more particularly the alkyl esters of an acrylic acid, e. g., themethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl,tert.-butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc., esters ofacrylic, methacrylic ethacrylic, phenylacrylic, etc., acids, includingthe alkyl acrylates containing not more than four carbon atoms in theester grouping, examples of which are given above, as Well as othervinyl aromatic and vinyl aliphatic compounds, and other compoundscontaining either a single CH2=C grouping or a plurality of CH2=Cgroupings. Other examples are given in, for instances, Thomas and KropaPatent No. 2,601,572, dated June 24, 1952, where examples are given bothby classes and species; see, for instance, column 11, line 54, throughline 35, column 12, of this patent.

Substantially insoluble, substantially infusible resins may be preparedby means of the chemical reaction or polymerization of a mixturecontaining a resin possessing a plurality of polymerizably reactivealpha-beta-enal groups (that is, the grouping enically unsaturatedpolycarboxylic compound, more particularly such a compound wherein theethylenically unsaturated grouping is alpha to a carbonyl group.

Among the reactive resins used in practicing my invention as a reactantwith an allyl compound of the kind embraced by Formula I are those whichare derived from r unsaturated alpha,beta-organic acids of the aliphaticseries and, therefore, contain the reactive groupings present in thoseacids. The terms unsaturated alpha,beta-organic acid andalpha,betaunsaturated organic acid, as commonly used in the art, do notinclude acids wherein the unsaturated grouping is part of anaromatic-acting radical, as for example phthalic acid, and the samedefinition -is adopted herein. Instead of the unsaturated polycarboxylicacids, the available anhydrides thereof also may be employed inproducing the unsaturated alkyd resin. The unsaturated alkyd resins arepreferably produced by the esteriiication of an unsaturatedalpha,betapolycarboxylic acid of the aliphatic series, more particularlyan alpha,beta-unsaturated polycarboxylic acid, with a polyhydricalcohol, and particularly a glycol. Although esterification of the acidwith a polyhydric alcohol is perhaps one of the simplest, mostconvenient ways of obtaining a reactive resin, I am not precluded fromusing resins otherwise derived from unsaturated alpha, beta-organicacids. I also may employ a crystalline unsaturated alkyd resin obtainedby the reaction of a glycol, which is completely symmetrical, with analpha, beta-unsaturated dicarboxylic acid having a transfiguration suchas fumaric acid. The unsaturated alkyd resin is preferably one having anacid number not greater than 50, although in some cases resins having anacid number as high as may be employed. The term unsaturated alkyd resinas used herein does not include within its meaning the conventionaldrying oilor drying oil acidmodified alkyd resins in the preparation ofwhich an aromatic or saturated aliphatic polycarboxylic acid oranhydride is used.

Illustrative examples of unsaturated alkyd resins that may be employedare those produced by reaction of the following ingredients: ethyleneglycol and maleic anhydride; glycerine and maleic anhydride; diethyleneglycol, maleic anhydride and phthalic anhydride; diethylene glycol anditaconic acid; ethylene glycol, maleic anhydride and succinic acid;ethylene glycol, maleic anhydride and tetrafiuorosuccinic acid; ethyleneglycol, itaconic acid and phthalic anhydride; diethylene glycol, maleicanhydride and tung oil acids; ethylene glycol, maleic anhydride, linseedoil acids and phthalic anhydride; diethylene glycol and maleicanhydride; ethylene glycol, maleic anhydride and stearic acid;diethylene glycol, maleic anhydride and decyl alcohol; ethylene glycol,maleic anhydride, octyl alcohol and acetic anhydride; diethylene glycol,fumaric acid, tetrahydroabietyl alcohol and linseed oil fatty acids;alpha-propylene glycol and maleic anhydride; diethylene glycol, fumaricacid and benzyl alcohol; diethylene glycol, fumaric acid andtetrahydroabietyl alcohol; ethylene glycol, fumaric acid andomega-hydroxydecanoic acid; diethylene glycol, fumaric acid and linseedoil fatty acid monoglycerides; etc. Reference is made to the followingpatents for more detailed information regarding the ingredients, thepreparation, and additional examples of modified and unmodifiedunsaturated alkyd resins that may be copolymerized with an allylcompound of the kind embraced by Formula I to yield new syntheticcompositions having a wide variety of commercial applications:2,409,633, 2,443,740, 2,443,741, 2,485,294, and 2,510,503.

Mixtures of any of the aforementioned polymerizable materials may becopolymerized with a single or with a plurality of allylmelamines orallylisomelamines of the kind embraced by Formula I. For example, I maycopolymerize with the allylmelamine or allylisomelamine an unsaturatedalkyd resin alone, e. g., diethylene glycol maleate, etc., or, alsoalone, a compound containing a CH2=C grouping (which compound isdifferent from the particular compound embraced by Formula I that isemployed in making the particular copolymer), e. g., styrene, diallylsuccinate, triallyl cyanurate, etc., or a mixture of such a resin andcompound. Mixtures of different unsaturated alkyd resins and ofdiiferent compounds containing a CH2=C grouping sometimes may beemployed advantageously in making a copolymer thereof with an allylcompound of the kind embraced by Formula I. Useful copolymercompositions also can be produced by copolymerization of diiferent allylcompounds of the kind within the scope of Formula I, for instance acopolymer of N-allylmelamine and N,N-diallylmelamine or a copolymer ofmonoallylisomelamine with N-allylmelamine, N,N-diallylrnelamine orN-allyl- N-phenylmelamine, or any of the other allylrnelamines embracedby Formula I or mixtures thereof. The latter copolymers can be usedadvantageously in modifying homopolymeric and copolymeric acrylonitrileto improve the dyeability of the latter, in which case they usuallyconstitute from about 1% to about 20% by weight of the blend ofpolymers.

Any suitable means may be used in effecting copolymerization of theallylmelamine and/ or -isomelamine with the reactant which iscopolymerizable therewith. Heat, light, or both heat and light, with orWithout a polymerization catalyst, can be used. A polymerizationcatalyst preferably is employed in order to shorten the period ofznraoos time required for polymerization of the mixture of ingredients.Any of the polymerization catalysts which are suitable for use inpolymerizing compounds containing an ethylenically unsaturated grouping,specifically a vinyl grouping, can be employed. Among such catalysts arethe inorganic peroxides, e. g., hydrogen peroxide, barium peroxide,magnesium peroxide, etc., and the various organic peroxy catalysts,illustrative examples of which latter are: the dialkyl peroxides, e. g.,diethyl peroxide, dipropyl peroxide, dibutyl peroxide, dilaurylperoxide, dioleyl peroxide, distearyl peroxide, di-(tert.-butyl)peroxide and di-(tert.-amyl) peroxide, such peroxides often beingdesignated as ethyl, propyl, butyl, lauryl, olcyl, stearyl, tert.-butyland tert.-amyl peroxides; the alkyl hydrogen peroxides, e. g.,tcrt.-butyl hydrogen peroxide (tert.-butyl hydroperoxide), tert.-amylhydrogen peroxide (tert.-amyl hydroperoxide), etc.; symmetrical diacylperoxides, for instance peroxides which commonly are known under suchnames as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoylperoxide, malonyl peroxide, succinyl peroxide, phthaloyl peroxide,benzoyl peroxide, etc; fatty oil acid peroxides, e. g., coconut oil acidperoxides, etc.; unsymmetrical or mixed diacyl peroxides, e. g., acetylbenzoyl peroxide, propionyl benzoyl peroxide, ctc.; terpene oxides, e.g., ascaridole, etc.; and salts of inorganic per-acids, e. g., ammoniumpersulfate, sodium persulfate, potassium per-sulfate, sodiumpercarbonate, potassium percarbonate, sodium perborate, potassiumperborate, sodium perphosphate, potassium perphospbate, etc. Otherexamples of organic peroxide catalysts that can be employed are thefollowing:

Tetralin hydroperoxide Tert.-butyl diperphthalate Cumene hydroperoxideTert.-butyl perbenzoate 2,4-dichlorobenzoyl peroxide Urea peroxideCaprylyl peroxide p-Chlorobenzoyl peroxide 2,2-bis(tcrt.-butyl peroxy)butane Hydroxyheptyl peroxide Diperoxide of benzaldehyde Other so-calledfree radical types of catalysts, e. g., or,a/azodiisobutyronitrile, canalso be used to accelerate polymerization.

If desired, the mixture of copolymerizable ingredients may bepolymerized in emulsion or in solution state to yield a copolymer. Goodresults are obtained by effecting copolymerization while the aforesaidingredients are dissolved in a suitable solvent, for example water or aliquid solvent comprising mainly water when the comonomer isacrylonitrile. Suitable inert organic solvents also can be used ifdesired, e. g., benzene, toluene, xylene, etc.

The polymerization also can be effected by conventional bu kpolymerization technique, in the presence or absence of a solventcapable of dissolving the copolymerizable mixture and in which thelatter preferably is inert; or by conventional bead polymerizationmethods. The polymerization of the mixture can be effected by acontinuous process as well as by a batch operation.

The concentration of the catalyst is relatively small, 0. g., from, byweight, about 1 part of catalyst per 1000 parts of the mixture ofcopolymerizablc ingredients to about 3 or 4 parts of catalyst per 100parts of the aforesaid mixture.

The temperature of polymerization of the polymerizable compositioncomprising an allylmelamine or -isomelamine of the kind with which thisinvention is concerned, and in the proportions specified in the secondparagraph of this specification, can be varied over a wide range, up toand including or slightly above the boiling point (at atmosphericpressure) of the polymerizablc mixture. In most cases, the polmerizationtemperature will be within the range of about or C., preferably at leastor 0., up to the boiling temperatre of the polymerizable mixture,depending, for example, upon the particular catalyst, if any, used, therapidity of polymer ization wanted and other influencing factors. Theuse of polymerization temperatures substantially above the boiling'point of the aforesaid mixture is not precluded, but

generally is less desirable because the polymerization reaction thenmust either be carried out in a closed reaction vessel under pressure,or, for economical reasons, with a reflux condenser or other meansprovided for the recovery and re-use of the volatilized monomer ormonomers if the reaction is carried out at the boiling temperature ofthe mass under atmospheric pressure.

If desired, the reactive ingredients may be copolymerized in thepresence of a plasticizer for the copolymer. Other copolymerizationmethods, however, also may be employed, e. g., methods such as thosedescribed in U. S. Patents 2,140,048, 2,160,054, 2,194,354, 2,333,635,2,436,926, and British Patent 586,881 with reference to the productionof other polymerization products.

If the copolymerization reaction is carried out while the mixedcopolymerizable ingredients are dissolved or dispersed in a liquidmedium, e. g., in solution in water, the resulting copolymer then isseparated from the said medium by any suitable means, e. g., byfiltration, centri- 1' uging, solvent extraction, etc.

In order that those skilled in the art may better understand how thepresent invention can be carried into effect, the following examples aregiven by way of illustration and not by way of limitation. All parts andpercentages are by weight.

Example 1 This example illustrates the preparation of homopolymericacrylonitrile, which is subsequently employed in comparative tests withcertain copolymers of the present invention.

A reaction vessel, equipped with a stirrer, reflux condenser,thermometer and gas-inlet tube, is placed in a constant-temperature bathwhich is maintained at 35 C. To the vessel is added a solution of 53.0parts of acrylonitrile, 900 parts of distilled water and 0.29 part ofsulfuric acid. The pH of the initial solution is 3.1. A rapid stream ofpre-purified nitrogen is passed over the surface of the solution for 30minutes. The nitrogen flow is then reduced to about one bubble persecond. A reduction-oxidation catalyst system (redox system) consistingof 1.71 parts of ammonium persulfate and 0.71 part of sodium bisulfite(meta), each dissolved in parts of water, is then added. The solutionfirst becomes cloudy at the end of 3 minutes, and the polymerization isfairly exothermic for the first half hour. The polymerization iscontinued for a total of 4 hours at 35 C. The polymer is collected on aBiichner funnel, and washed with 1,000 parts of distilled water followedby about 160 parts of methanol. The polymer is dried in an oven at C.for about 16 hours. The yield of dry polyacrylonitrile, which is white,amounts to 48 parts.

Example 2 A reaction vessel, equipped with a stirrer, reflux condenesr,thermometer and gas-inlet tube, is placed in a constant-temperature bathwhich is maintained at 35 C. To the vessel is added a solution of 50.35parts of acrylonitrile, 2.65 parts of N,N-diallylmelamine, 900 parts ofdistilled water and 0.65 part of sulfuric acid. The pH of the resultingsolution is 3.0. A rapid stream of prepurified nitrogen is passed overthe surface of the solution for 30 minutes. The nitrogen flow is thenreduced to about one bubble per second. To the vessel is then added 1.71parts of ammonium persulfate and 0.36 part of sodium bisulfite (meta),each dissolved in 50 parts of water. The polymerization is carried outfor 4 hours at 35 C. The resulting copolymer of acrylonitrile' andN,N-diallylmelamine is collected on a Biichner funnel, washed with 1000parts of deionized water and then '9 dried in an oven at 70 C. for about16 hours. The yield of dry, white copolymer amounts to 40.2 parts.

Example 3 Same as in Example 2 with the exception that 2.65 parts ofmethyl acrylate used in addition to the 50.35 parts of acrylonitrile and2.65 parts of N,N-diallylmelamine; and 0.71 part, instead of 0.36 part,of sodium bisulfite (meta) is employed. A good yield of a threecomponentcopolymer of acrylonitrile, N,N-diallylmelamine and methyl acrylate isobtained.

Example 4 Same as in Example 2 with the exception that, instead of 2.65parts of N,N-diallylmelamine, there is used 2.65 parts ofN,N',N"-triallylmelamine. Similar results are obtained.

Example 5 Same as in Example 2 with the exception that the N,N-diallylmelarnine is replaced by the same amount of N,N'-diallylmelamine. A good yield of a copolymer of acrylonitrile andN,N-diallylmelamine is obtained.

Example 6 Same as in Example 2 with the exception that 47.7 parts ofacrylonitrile and 5.3 parts of N,N-diallylme1amine are used instead ofthe proportions of these comonomers specified in that example; also,0.71 part, instead of 0.36 part, of sodium bisulfite (meta) is employed.Similar results are obtained.

Example 7 Example 8 Essentially the same conditions and procedure areemployed as in Example 2 with the exception that the N,N-diallylmelamine is replaced with an equal weight of N-allyl-N-methylmelamine, and the polymerization time is 6 hours at 35 C.A good yield of a white, dry copolymer of acrylonitrile andN-allyl-N-methylmelamine is obtained.

Example 9 Same as in Example 2 with the exception that 2.65 parts ofN-allyl-N-cyclohexylmelamine is used instead of 2.65 parts ofN,N-diallylmelamine, and the polymerization time is 6 hours at 35 C.Similar results areobtained.

Example 10 Same as in Example 2 with the exception that 47.7 parts ofacrylonitrile, 2.65 parts of N-allyl-N-benzylmelamine and 2.65 parts ofacrylamide are used instead of 50.35 parts of acrylonitrile and 2.65parts of N,N-diallylmelamine; also 0.71 part, in place of 0.36 part, ofsodium bisulfite (meta) is employed. A good yield of a threecomponentcopolymer of acrylonitrile, acrylamide and N- allyl-N-benzylmelamine isobtained.

Example 11 Q Same as in Example 2 with the exception that 47.7 parts ofacrylonitrile and 5.3 parts of N-allyl-N-tolylmelamine are used insteadof 50.35 parts of acrylonitrile and 2.65 parts of N,N-diallylmelamine;and 0.71 part, instead of 0.36 part, of sodium bisulfite (meta). A goodyield of a copolymer of acrylonitrile and N-allyl-N-tolylmelamine isobtained.

10 Example 12 Essentially the same conditions and procedure are employedas in Example 2 with the exception that the N,N-

diallylmelamine is replaced with an equal weight of N- Example 13 l nthis example, too, the conditions and procedure are essentially the sameas in Example 2 with the exception that the N,N-diallylmelamine isreplaced with an equal weight of allylisomelamine (N-allylisomelamine)and the polymerization time is 5 hours at 35 C. The yield of dry,-whitecopolymer of acrylonitrile and N-monoallylisomelamine(N-allylisomelamine) amounts to 48.5 parts.

N-allylisomelamine is prepared, for example, by heating together for 5hours at 95 -98 C. a mixture of equal molar proportions of allylaminehydrochloride, ammonium chloride and monopotassium 1,3-dicyanoguanidine.The mixture becomes fluid after 10 minutes heating and slowlysolidifies. The temperature is raised to 180 C. by heating the reactionvessel in an oil bath, and heating is continued at that temperature for16 hours. At the end of the reaction period the cake is broken up anddissolved in. 1 liter of boiling water containing ml. of concentratedhydrochloric acid. After treatment with decolorizing carbon, thesolution is filtered and cooled. The allylisomelamine(N-allylisomelamine) which separates melts at 184 C. with decompositon.

Example 14 Samples of the homopolymeric acrylonitrile of Example 1 andof the copolymers of Examples 2 to 13, inclusive, are subjected to thefollowing dye test:

A sample (5 parts) of the dry polymer or copolymer (ground in a mill topass through a 20-mesh screen) is added to a dye bath consisting of 500parts of an aqueous solution containing 0.2 part of concentratedsulfuric acid, 1 part of sodium sulfate and 0.2 part of CalcocidAlizarine Blue SAPG (Color Index No. 1054). The dye bath is boiled forminutes, after Which the polymerization product is filtered off andwashed with hot water until the water is free of dye. The copolymers ofExamples 2 to 13, inclusive, are dyed blue, theacrylonitrile-allylisomelamine copolymer of Example 13 being a lighterblue than that of Examples 2l2. In marked contrast, no dye is absorbedby the homopolymeric acrylonitrile of Example 1. The advantage ofreplacing a part (e. g., from about 1% to about 20% or more, still moreparticularly from 1 or 2% to 5 or 10 or 15%) of the initialacrylonitrile with an allylmelamine and/ or allylisomelamine of the kindwith which this invention is concerned, thereby to obtain a copolymericacrylonitrile substance of improved dyeability, is therefore quiteapparent.

Other modifying monomers, in addition to the methyl acrylate named inExample 3 and the acrylamide specified in Example 10, can be used.Numerous examples of such comonomers have been given hereinbefore. Theproportions of any modifying comonomer or comonomers that areincorporated in the polymerizable compositon together with theacrylonitrile and the allylmelamine and/ or -isomelamine can be variedas desired or as conditions may require. Ordinarily, however, theacrylonitrile constitutes a major or preponderant proportion (more thanby weight of the total Weight of monomers to be copolymerized, the allylcompound constitutes from about 1% to about 20% of the total weight ofthe acrylonitrile and allyl compound, and any modifying comonomer orcomonomers (if present in the polymerizable mixture) constitute theremainder of the total amount of comonomers which are subjected tocopolymerization.

In the preferred acrylonitrile copolymer compositions (more particularlythermoplastic acrylonitrile copolymer compositions) of the presentinvention, the acrylonitrile is employed in the mixture of comonomers inan amount such that at least 85% by weight of combined acrylonitrile ispresent in the copolymer. When the polymerize tion rates of theacrylonitrile and additional monomer or monomers are ditferent from eachother, then it may be necessary to start with an amount of acrylonitrileeither more or less than 85% by weight of the total mixture of monomersin order that the final copolymer will contain at least 85% by Weight ofcombined acrylonitrile in the copolymer molecule. Similarly, in orderthat the finished copolymer shall contain, in the copolymer molecule,from about 1% to about 20% by weight of combined allylmelamine and/ or-isomelarnine, preferably between about 2 or 3% and about or it may benecessary to start with an amount of the allyl compound, either" more orless than that which is present in the finished copolymer in order thatthe said copolymer will have the ultimate composition desired orrequired in order to impart optimum dye receptivity thereto.

Example 15 The N-monoallylyisomelamine hydrochloride and acrylamide aredissolved in the water, and then heated in a reaction vessel, providedwith a reflux condenser, on a steam bath. The resulting clear solutionis brought from a temperature of 50 C. to 75 C. in 7 minutes, afterwhich the ammonium persulfate is added and the reaction mass is broughtto reflux temperature (90-91 C.) in 3 minutes, and is heated at thattemperature for 2% hours. After standing for about 16 hours, a clearsyrup results. This syrupy copolymerization product is poured into 4,000parts of methanol, yielding a white precipitate. On airdrying, the massdarkens and separates into a gummy phase comprising a copolymer ofacrylamide and the allyl compound (probably mostly in the form ofcombined N- monoallylisornelamine hydrochloride) and a clear liquidcomprising a mixture of water and methanol. The liquid is poured off andthe gummy copolymer is dried for about 16 hours at 110 C., yielding, atan-colored solid comprising the aforementioned copolymerx, Thiscopolymer is suitable for use as a component of textile-finishingcompositions, e. g., warp-sizing compositions.

Example 16 Parts N-monoallylmelamine (N-allylmelamine) 60.0 Styrene 40.0Monomethyl ether of ethylene glycol 200.0 Cumene hydroperoxide 5.0

The N-allyhnelamine is added to the boiling ethylene gylcol monomethylether, all but a trace of the allyl compound dissolving in the saidsolvent. The styrene is added to the solution of the allyl compound,after which 1 part of the cumene hydroperoxide is added, and thesolution is heated under reflux for 2 hours. After standing for about 16hours, another 2 parts of the curnene hydroperoxide is added andrefluxing is continued for another 6 /2 hours, the remainder (2 parts)of the hydroperoxide being added after refluxing has proceeded for 1%hours. The. resulting dark syrup comprising a copolymer of styrene andN- aliyl-melamine is poured into 4,000 parts of methanol, whereupon thecopolymer precipitates as a tan-colored solid, which is filtered oil,washed with methanol and airdried. The dry product is a soft, tan powderwhich may be used as a modifier of other synthetic materials, e. g.,thermosetting aminoplasts such, for instance, as ureaformaldehyderesins, melamine-formaldehyde resins, ureamelamine-formaldehyde resins,etc.

Example I 7 Parts" N,N-diallylmelamine 20.0

Unsaturated alkyd resin produced by reaction of 6.6 moles propyleneglycol, 2.0 moles of phthalic anhydride and 4.0 moles of maleicanhydride 40.0

Benzoyl peroxide 1.0

Example 18' Parts N',N-diallylmelamine 20.0 Dialiyl phthalate 20.0Di-(tert-butyl) peroxide 1.0

The two allyl compounds are heated together in a reaction vessel to 150C., at which temperature the peroxide polymerization catalyst is added.A gel comprising a copolymer of the N,N-diallylmelamine and diallylphthalate is obtained. This gel may be used to thicken oils and otherliquids.

Example 19 Parts l-I,N-diallylmelamine 10.0 Diallyl phthalate 40.0Di-(tert.-butyl) peroxide 2.0

The same procedure is followed as described under Example 18 with theexception that, after adding the peroxide catalyst, heating of themixture is continued at 150-155 C. Within about 4 to 5 minutes, avigorous polymerization occurs and the mass sets to a stiff, fairlyclear, amber-colored gel comprising a copolymer of the aforementionedallyl compounds. The polymerizable composition of this example may becast and polymerized to yield a hard, cast resin; or it may be mixedwith fillers and employed, for example, as a potting compound,thereafter being polymerized in situ.

Example 20 Parts Methyl methacrylate 40.0 N,N-diallylmelamine 10.0 50%aqueous dispersion of gamma-stearamidopropylbeta-hydroxyethyldimethylammonium chloride 5.0 Water 200.0

HCl (used in the form of aqueous 12N HCl) 1.75

To the mixture of the first four ingredients in a suitable reactionvessel is added the aqueous HCl (nearly one equivalent) whichfacilitates dissolution of the N,N-diallylmelamine. After next adding0.10 part of (NH4)2SzOa, the mixture is heated on a steam bath for 2hours, yielding a stable latex. The copolymer of methyl methacrylate andN,N-diallylmelarnine is precipitated by adding isopropyl alcohol, afterwhich it is filtered off, washed with isopropyl alcohol and dried toyield a white powder. A sample of the latex contained 21.5% of solidswhen determined by evaporation of the sample on a steam bath, then driedfor 1 hour at C. The dried copolymeric material is hard, clear andbrittle, and is insoluble in ethyl acetate. It is suitable for use as aflatting agent in varnishes and lacquers.

Example 21 Essentially the same as in Example 2 with the exception that26.5 parts each of acrylonitrile and N,N-diallylmelamine are used and7.2 parts instead of 0.65 part of Example 22 Same as in Example 17 withthe exception that, in addition to 20 parts of N,N-dial1ylmelamine and40 parts of unsaturated alkyd resin, there is used parts ofapproximately a 50-50 mixture of oand p-methylstyrenes; also, 2 partsinstead of 1 part of benzoyl peroxide is employed. Similar results areobtained.

The polymerizable compositions and copolymers of this invention havenumerous applications in the plastics, coating, laminating, adhesive,impregnating, electrically. insulating, casting, fiber-forming and otherarts. For instance, with or without a filler or other additive, they maybe used as molding compositions (or as components of moldingcompositions) from which molded articles are produced by molding thecompositions under heat and pressure, e. g., at temperatures of theorder of 130 C. or 140 C. to 200 C. and under pressures up to 10,000pounds or more per square inch. Among the fillers that can be employedin the production of molding compositions are alpha-cellulose pulp,asbestos fibers, cotton flock, chopped cloth cuttings, glass fibers,wood flour, antimony oxide, titanium dioxide, sand, clay, mica dust,diatomaceous earth, etc.

The polymerizable compositions of my invention can be used in theproduction of castings of any desired shape or size; as adhesives; inthe treatment of paper or paper stock; in coating compositions; and forvarious other purposes. The copolymer can be formed in situ afterapplication of the polymerizable mixture to the base material to becoated, impregnated or otherwise treated.

Fibers can be produced from certain of the copolymers of the presentinvention, for example the acrylonitrile copolymers, in the mannerdescribed in, for example, Patents 2,558,730, 2,558,731 and 2,558,733.The unoriented and oriented fibers produced from my new copolymers arereadily dyed, especially with an acid dye, while the fiber is in eithera gel (e. g., hydrogel or aquagel) or a dry state.

In a manner similar to that described hereinbefore with reference to theproduction of copolymers of an allylmelamine or allylisomelamine of thekind hereinbefore described, other copolymers can be produced by usingother compounds embraced by the following broader, general formula:

where at least one and not more than three of the Rs represent anethylenically unsaturated, aliphatic, hydrocarbon radical containing atleast three and not more than ten carbon atoms, and the remaining Rs area member of the class consisting of hydrogen and alkyl cycloalkyl, aryl(including alkaryl) and aralkyl radicals, or an isomelaminecorresponding to the melamines of Formula V, or mixtures of suchmelamines and isomelamines. Illustrative examples of ethylenicallyunsaturated, aliphatic, hydrocarbon radicals which are embraced by thisbroader definition of R are: allyl, methallyl, ethallyl,

propallyl, 2-butenyI, 3-butenyl, 3-methyl-2-butenyl, 3'-methyl-S-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-methyl-Z-pentenyl, 3-methyl-4-pentenyl, 2-hexenyl, 2,3- pentadienyl,2,4-hexadienyl, 2-octenyl, 3-nonenyl, 2- decenyl, etc. The kinds andproportions of copolymerizable ingredients employed are the same asthose given hereinbefore.

I claim:

1. A polymerizable composition comprising (1) a compound of the class ofcompounds consisting of (a) melamines represented by the general formulaR R K R N N R at t p where at least one and not more than three of theRs represent the radical CHzCH=CH2 and the remaining Rs are a member ofthe class consisting of hydrogen and alkyl, cycloalkyl, aryl and aralkylradicals, and (b) isomelamines corresponding to the melamines of (a),and (2) a substance which is difierent from the compound of (l), whichis copolyrnerizable therewith, and which is selected from the class ofunsaturated substances consisting of (A) compounds containing a CH2=Cgrouping, (B) unsaturated alkyd resins produced 'by reaction ofingredients comprising a polyhydric alcohol and an ethylenicallyunsaturated polycarboxylic compound wherein the only grouping presenttherein which is reactive with a polyhydric alcohol is an esterifiablecarboxy grouping, and (C) mixtures of (A) and (B), the compound of (l)constituting from about 1% to about by weight of the total amount of (l)and (2).

2. A polymerizable composition as in claim 1 wherein the substance of(2) is a vinyl compound.

3. A polymerizable composition as in claim 2 wherein the vinyl compoundis a vinyl aliphatic compound.

4. A polymerizable composition as in claim 3 wherein the vinyl aliphaticcompound is acrylonitrile.

5. A polymerizable composition as in claim 2 wherein the vinyl compoundis a vinyl aromatic compound.

6. A polymerizable composition as in claim 5 wherein the vinyl aromaticcompound is styrene.

7. A product comprising the polymerized composition of claim 1.

8. A product comprising the polymerized composition of claim 2.

9. A product comprising the polymerized composition of claim 3.

10. A product comprising the polymerized composition of claim 4.

11. A product comprising the polymerized composition of claim 5.

12. A product comprising the polymerized composition of claim 6.

13. A polymerizable composition comprising 1) acrylonitrile and (2) acompound of the class of compounds consisting of (a) melaminesrepresented by the general formula where at least one and not more thanthree of the Rs represent the radical --CH2CH CHz and the remaining Rsare a member of the class consisting of hydrogen and alkyl, cycloalkyl,aryl and aralkyl radicals, and b) isomelamines corresponding to themelamines of (a),

the compoundof (2) constituting from about 1% to about 20%. by weight ofthe total amount of (1) and (2'). e 1 4. A product comprising thepolymerized composition of claim 13.

15. A composition comprising a copolymer of a mixture containing (1)acrylonitrile and (2) a compound of the class of compounds consisting of(a) melamines represented by the general formula where at least one andnot more than three of the Rs represent the radical -CH2.CH=CH2 and theremaining Rs are a member of the class consisting of hydrogen and alkyl,cycloalky], aryl and aralkyl radicals, and (b') isornelaminescorresponding to the melamines of (a), the compound of (2) constitutingfrom about 1% to about 15% by weight of the total amount of (1) and (2).

16. A composition as in claim 15 wherein the compound of (2) isN-rnonoallylmelamine.

17. A composition as in claim 15 wherein the compound of. (2) isN,N-diallylmelamine.

18. A composition as in claim 15 wherein the compound of (2) isN-allyl-N-phenylmelamine.

19. A composition as in claim 15 wherein the compound of (2) is.monoallylisomelamine.

. 20'. The method of preparing a new copolymer which comprisespolymerizing, with the aid of a polymerization catalyst, a mixture ofcopolymerizable ingredients including (1) a compound of the class ofcompounds consisting of (.a) melamines represented by the generalformula where at least one and not more than three of the Rs representthe radical. --CH2-CH=CHZ and the remaining R.s' are a member of theclass consisting of hydrogen and alkyl, cycloalkyl, aryl and aralkylradicals, and (b) isomelamines corresponding to the melamines of (a),and (2) a substance which is different from the compound of (1), whichis copolymerizablc therewith, and which is selected from the class ofunsaturated substances consisting. of (A) compounds containing a CH2=Cgrouping, (B) unsaturated alkyd resins produced by reaction ofingredients comprising a polyhydric alchohol and an ethylenicallyunsaturated polycarboxylic compound wherein the only grouping presenttherein which is reactive with a polyhydric alchol is an esterifiablecarboxy grouping, and (C) mixtures of (A) and (B), the compound of (1')constituting from about 1% to about by weight of the total amount of 1)and (2).

21. The method of preparing a new copolymer which comprises polymerizingin an aqueous medium, with the aid of a polymerization catalyst, amixture of copolymerizable ingredients including (1) acrylonitrile and(2) a compound of the class of compounds consisting of (a) melaminesrepresented by thegeneral formula where at least one and not more thanthree of the Rs represent the radical --CHz-CH=CHz and the remaining Rsare amember of the class consisting of hydrogen and alkyl, cycloalkyl,aryl and aralkyl radicals, and (b) isomel'amines corresponding to themelamines of (a), the compound of (2) constituting from about 1% toabout 20% by weight of the total amount of (1) and (2).

References Cited in the file of this patent Cyanamid New ProductBulletin-N,N-Diallylmelamine, pages 1 and 8, pub. March 1951 by Am.Cynamid Co.

1. A POLYMERIZABLE COMPOSITION COMPRISING (1) A COMPOUND OF THE CLASS OFCOMPOUNDS CONSISTING OF (A) MELAMINES REPRESENTED BY THE GENERAL FORMULA